A. Technical Field
The present invention relates to a novel water-soluble copolymer, and its production process and use.
B. Background Art
Water-soluble polymers are preferably used as detergent builders, pigment dispersants, and scale inhibitors. Examples thereof as well known conventionally includes (co)polymers of unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, xcex1-hydroxyacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and citraconic acid.
Furthermore, the study of improving the (co)polymers is extensively carried out in recent years for the purpose of raising the performance for uses such as detergent builders, pigment dispersants, and scale inhibitors.
As to copolymers having particularly excellent improvement of performance, JP-B-68323/1992 discloses a binary copolymer of a specific unsaturated alcoholic monomer and a specific unsaturated carboxylic acid monomer.
However, it is not said that the above binary copolymer has still sufficient performance for uses, such as detergent builders, pigment dispersants, and scale inhibitors, and it is desired to raise the performance further.
In addition, detergent builders comprising the above conventional unsaturated carboxylic acid (co)polymer and its improved material as a base material could display comparatively high-level performance.
However, the detergent builders comprising the conventional unsaturated carboxylic acid (co)polymer have extremely bad compatibility with surfactants, therefore, there were disadvantages in that the detergent builder was not suitable for liquid detergent use.
A. Object of the Invention
Accordingly, an object of the present invention is to provide: a novel water-soluble copolymer which is still more excellent in performance for uses, such as detergent builders, pigment dispersants, and scale inhibitors.
In addition, another object of the present invention is to provide: a novel liquid detergent builder which has extremely excellent compatibility, high transparency when a liquid detergent composition comprises it, and very excellent detergency; and a novel liquid detergent composition comprising the liquid detergent builder.
B. Disclosure of the Invention
The present inventors diligently studied to solve the problems. As a result, they used two kinds of specific unsaturated carboxylic acid monomers, namely, used an unsaturated monocarboxylic acid monomer together with an unsaturated dicarboxylic acid monomer, and aimed at a novel trinary or quaternary or more water-soluble copolymer obtained by copolymerizing comonomers including these two kinds of unsaturated carboxylic acid monomers and a specific unsaturated alcoholic monomer. Then, they aimed at the residual amount of the raw monomers in this copolymer, and found that the copolymer can display still more excellent performance for uses, such as detergent builders, pigment dispersants, and scale inhibitors than conventional ones in case that the residual amounts of the unsaturated dicarboxylic acid monomer and the unsaturated alcoholic monomer are in the range of not more than predetermined levels. In addition, they found that the copolymer can display still more excellent performance for uses, such as detergent builders, pigment dispersants, and scale inhibitors than conventional ones in case that the clay dispersibility of the copolymer is not less than a predetermined level. The present invention was completed in this way.
The present inventors aimed at water-soluble copolymers obtained by copolymerizing comonomers including a specific unsaturated carboxylic acid monomer and a specific unsaturated alcoholic monomer. Then, they found that: the above object which could not be solved by the builder comprising the conventional unsaturated carboxylic acid (co)polymer can perfectly be solved by using the above specific water-soluble copolymers as liquid detergent builders. The present invention was completed in this way.
That is to say, a novel water-soluble copolymer, according to the present invention, is obtained by copolymerizing comonomers essentially including: an unsaturated monocarboxylic acid monomer (1) as represented by a general formula (1) below; an unsaturated dicarboxylic acid monomer (2a) as represented by a general formula (2a) below and/or an unsaturated dicarboxylic acid monomer (2b) as represented by a general formula (2b) below; and an unsaturated alcoholic monomer (3) as represented by a general formula (3) below,
with the copolymer being characterized in that: the residual amount of the unsaturated dicarboxylic acid monomer is not more than 8 weight %, and the residual amount of the unsaturated alcoholic monomer is not more than 45 weight %,
wherein the general formula (1) is: 
where: A1, A2, and A3 each independently represent a hydrogen atom or a methyl group; and X1 represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group;
wherein the general formula (2a) is: 
where: A4 and A5 each independently represent a hydrogen atom, a methyl group, or xe2x80x94COOX3; A6 represents a hydrogen atom, a methyl group, or xe2x80x94CH2COOX4; only any one of A4, A5, and A6 is xe2x80x94COOX3 or xe2x80x94CH2COOX4; and X2, X3, and X4 each independently or together represent a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group;
wherein the general formula (2b) is: 
where: A7 and A8 each independently represent a hydrogen atom or a methyl group; and
wherein the general formula (3) is: 
where: R1, R2 and R4 each independently represent a hydrogen atom or a methyl group, and R1 (or R4) and R2 are not simultaneously methyl groups; and R3 represents xe2x80x94CH2xe2x80x94, xe2x80x94(CH2)2xe2x80x94, or xe2x80x94C(CH3)2xe2x80x94, and the total carbon atoms contained in R1, R2, R3 and R4 is 3; Y represents an alkylene group having 2 to 18 carbon atoms; and n is an integer of 1 to 300.
In addition, another novel water-soluble copolymer, according to the present invention, is obtained by copolymerizing comonomers essentially including: an unsaturated monocarboxylic acid monomer (1) as represented by a general formula (1) below; an unsaturated dicarboxylic acid monomer (2a) as represented by a general formula (2a) below and/or an unsaturated dicarboxylic acid monomer (2b) as represented by a general formula (2b) below; and an unsaturated alcoholic monomer (3) as represented by a general formula (3) below,
with the copolymer being characterized by having a clay dispersibility (50 ppm of calcium carbonate) of not less than 0.7,
wherein the general formula (1) is: 
where: A1, A2, and A3 each independently represent a hydrogen atom or a methyl group; and X1 represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group;
wherein the general formula (2a) is: 
where: A4 and A5 each independently represent a hydrogen atom, a methyl group, or xe2x80x94COOX3; A6 represents a hydrogen atom, a methyl group, or xe2x80x94CH2COOX4; only any one of A4, A5, and A6 is xe2x80x94COOX3 or xe2x80x94CH2COOX4; and X2, X3, and X4 each independently or together represent a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group;
wherein the general formula (2b) is: 
where: A7 and A8 each independently represent a hydrogen atom or a methyl group; and
wherein the general formula (3) is: 
where: R1, R2 and R4 each independently represent a hydrogen atom or a methyl group, and R1 (or R4) and R2 are not simultaneously methyl groups; and R3 represents xe2x80x94CH2xe2x80x94, xe2x80x94(CH2)2xe2x80x94, or xe2x80x94C(CH3)2xe2x80x94, and the total carbon atoms contained in R1, R2, R3 and R4 is 3; Y represents an alkylene group having 2 to 18 carbon atoms; and n is an integer of 1 to 300.
In addition, a production process for a novel water-soluble copolymer essentially comprising: a constitutional unit (4) as represented by a general formula (4) below; a constitutional unit (5) as represented by a general formula (5) below; and a constitutional unit (6) as represented by a general formula (6) below, according to the present invention, is characterized by carrying out a copolymerization of comonomers essentially including: an unsaturated monocarboxylic acid monomer (1) as represented by a general formula (1) below; an unsaturated dicarboxylic acid monomer (2a) as represented by a general formula (2a) below and/or an unsaturated dicarboxylic acid monomer (2b) as represented by a general formula (2b) below; and an unsaturated alcoholic monomer (3) as represented by a general formula (3) below,
wherein the general formula (4) is: 
where: A1, A2, and A3 each independently represent a hydrogen atom or a methyl group; and X1 represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group;
wherein the general formula (5) is: 
where: A4 and A5 each independently represent a hydrogen atom, a methyl group, or xe2x80x94COOX3; A6 represents a hydrogen atom, a methyl group, or xe2x80x94CH2COOX4; only any one of A4, A5, and A6 is xe2x80x94COOX3 or xe2x80x94CH2COOX4; and X2, X3, and X4 each independently or together represent a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group;
wherein the general formula (6) is: 
where: R1, R2 and R4 each independently represent a hydrogen atom or a methyl group, and R1 (or R4) and R2 are not simultaneously methyl groups; and R3 represents xe2x80x94CH2xe2x80x94, xe2x80x94(CH2)2xe2x80x94, or xe2x80x94C(CH3)2xe2x80x94, and the total carbon atoms contained in R1, R2, R3 and R4 is 3; Y represents an alkylene group having 2 to 18 carbon atoms; and n is an integer of 1 to 300;
wherein the general formula (1) is: 
where: A1, A2, and A3 each independently represent a hydrogen atom or a methyl group; and X1 represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group;
wherein the general formula (2a) is: 
where: A4 and A5 each independently represent a hydrogen atom, a methyl group, or xe2x80x94COOX3; A6 represents a hydrogen atom, a methyl group, or xe2x80x94CH2COOX4; only any one of A4, A5, and A6 is xe2x80x94COOX3 or xe2x80x94CH2COOX4; and X2, X3, and X4 each independently or together represent a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group;
wherein the general formula (2b) is: 
where: A7 and A8 each independently represent a hydrogen atom or a methyl group; and
wherein the general formula (3) is: 
where: R1, R2 and R4 each independently represent a hydrogen atom or a methyl group, and R1 (or R4) and R2 are not simultaneously methyl groups; and R3 represents xe2x80x94CH2xe2x80x94, xe2x80x94(CH2)2xe2x80x94, or xe2x80x94C(CH3)2xe2x80x94, and the total carbon atoms contained in R1, R2, R3 and R4 is 3; Y represents an alkylene group having 2 to 18 carbon atoms; and n is an integer of 1 to 300.
Furthermore, a detergent builder, according to the present invention, is characterized by essentially including the novel water-soluble copolymer according to the present invention. In addition, a detergent composition, according to the present invention, is characterized by comprising the detergent builder according to the present invention.
In addition, a pigment dispersant, according to the present invention, is characterized by essentially comprising the novel water-soluble copolymer according to the present invention.
Furthermore, a scale inhibitor, according to the present invention, is characterized by essentially comprising the novel water-soluble copolymer according to the present invention.
Furthermore, a liquid detergent builder, according to the present invention, comprises a water-soluble copolymer obtained by copolymerizing comonomers essentially including an unsaturated carboxylic acid monomer (a) and an unsaturated alcoholic monomer as represented by general formula (3) below,
wherein the unsaturated carboxylic acid monomer (a) is any one of an unsaturated monocarboxylic acid monomer (1) as represented by a general formula (1) below, an unsaturated dicarboxylic acid monomer (2a) as represented by a general formula (2a) below, and an unsaturated dicarboxylic acid monomer (2b) as represented by a general formula (2b) below,
wherein the general formula (1) is: 
where: A1, A2, and A3 each independently represent a hydrogen atom or a methyl group; and X1 represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group;
where the general formula (2a) is: 
where A4 and A5 each independently represent a hydrogen atom, a methyl group, or xe2x80x94COOX3; A6represents a hydrogen atom, a methyl group, or xe2x80x94CH2COOX4; only any one of A4, A5, and A6 is xe2x80x94COOX3 or xe2x80x94CH2COOX4; and X2, X3 , and X4 each independently or together represent a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group;
wherein the general formula (2b) is: 
where: A7 and A8 each independently represent a hydrogen atom or a methyl group; and
wherein the general formula (3) is: 
where: R1, R2 and R4 each independently represent a hydrogen atom or a methyl group, and R1 (or R1) and R1 are not simultaneously methyl groups; and R3 represents xe2x80x94CH2xe2x80x94, xe2x80x94(CH2)2xe2x80x94, or xe2x80x94C(CH3)2xe2x80x94, and the total carbon atoms contained in R1, R2, R3 and R4 is 3; Y represents an alkylene group having 2 to 18 carbon atoms; and n is an integer of 1 to 300.
In addition, a liquid detergent composition, according to the present invention, comprises the liquid detergent builder according to the present invention.
These and other objects and the advantages of the present invention will be more fully apparent from the following detailed disclosure.
[Novel Water-Soluble Copolymer]
The unsaturated monocarboxylic acid monomer (1) which can be used in the present invention is not especially limited if it can be represented by the general formula (1). Examples thereof include: acrylic acid, methacrylic acid, crotonic acid, their monovalent metal salts, or partially or completely neutralized products with ammonia or organic amines.
The unsaturated dicarboxylic acid monomer (2a) or (2b) which can be used in the present invention is not especially limited in the present invention if it can be represented by the general formula (2a) or (2b). Examples of the monomer which can be represented by the general formula (2a) includes: maleic acid, fumaric acid, crotonic acid, citraconic acid, their monovalent metal salts, or partially or completely neutralized products with ammonia or organic amines. In addition, examples of the monomer which can be represented by the general formula (2b) include: unsaturated dicarboxylic acid anhydride monomers such as maleic anhydride or citraconic anhydride, but are not especially limited to these.
The unsaturated alcoholic monomer (3) which can be used in the present invention is not especially limited if it can be represented by the general formula (3). Examples thereof includes: compounds obtained by adding 1 to 300 moles (preferably 1 to 100 moles, more preferably 5 to 50 moles) of an alkylene oxide having 2 to 18 carbon atoms to 1 mol of unsaturated alcohols, such as 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, or 2-methyl-3-buten-2-ol. Examples of the alkylene oxide having 2 to 18 carbon atoms include: styrene oxide, ethylene oxide, and propylene oxide. The ethylene oxide and/or propylene oxide is preferably used. When the ethylene oxide is combined with the propylene oxide, the combining turn is not limited.
In case where the addition number of moles of the ethylene oxide and/or propylene oxide is 0, the effects of the present invention cannot be displayed enough. In addition, in case where the addition number exceeds 300, there are disadvantages in that the effects of the present invention is not improved, and it is merely necessary to add too much.
The novel water-soluble copolymer according to the present invention is obtained by copolymerizing comonomers essentially including the unsaturated monocarboxylic acid monomer (1), the unsaturated dicarboxylic acid monomer (2a) and/or (2b), and the unsaturated alcoholic monomer (3). However, the comonomers may include other copolymerizable monomers with the monomers (1) to (3) in addition to the monomers (1) to (3).
The other monomers are not especially limited, but examples thereof include: styrene; styrenesulfonic acid; vinyl acetate; (meth)acrylonitrile; (meth)acrylamide; methyl (meth)acrylate; ethyl (meth)acrylate; butyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; dimethylamino (meth)acrylate; diethylamino (meth)acrylate; allyl alcohol; 3-methyl-3-buten-1-ol; 3-methyl-2-buten-1-ol; 2-methyl-3-buten-2-ol; 3-(meth)acryloxy-1,2-dihydroxypropane; 3-(meth)acryloxy-1,2-di(poly)oxyethylene ether propane; 3-(meth)acryloxy-1,2-di(poly)oxypropylene ether propane; 3-(meth)acryloxy-1,2-dihydroxypropanesulfate, and its monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts, or its mono- or di-ester of alkyl groups having 1 to 4 carbon atoms; 3-(meth)acryloxy-1,2-dihydroxypropanesulfonic acid, and its monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts, or its mono- or di-ester of alkyl groups having 1 to 4 carbon atoms; 3-(meth)acryloxy-2-(poly)oxyethylene ether propanesulfonic acid, and its monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts, or its mono- or di-ester of alkyl groups having 1 to 4 carbon atoms; 3-(meth)acryloxy-2-(poly)oxypropylene ether propanesulfonic acid, and its monovalent metal salts, divalent metal salts, ammonium salts, or organic amine salts, or its mono- or di-ester of alkyl groups having 1 to 4 carbon atoms; 3-allyloxypropane-1,2-diol; 3-allyloxypropane-1,2-diol phosphate; 3-allyloxypropane-1,2-diol sulfonate; 3-allyloxypropane-1,2-diol sulfate; 3-allyloxypropane-1,2-di(poly)oxyethylene ether propane; 3-allyloxypropane-1,2-di(poly)oxyethylene ether propanephosphate; 3-allyloxypropane-1,2-di(poly)oxyethylene ether propanesulfonate; 3-allyloxypropane-1,2-di(poly)oxypropylene ether propane; 3-allyloxypropane-1,2-di(poly)oxypropylene ether propanephosphate; 3-allyloxypropane-1,2-di(poly)oxypropylene ether propanesulfonate; 6-allyoxyhexane-1,2,3,4,5-pentaol; 6-allyoxyhexane-1,2,3,4,5-pentaolphosphate; 6-allyoxyhexane-1,2,3,4,5-pentaolsulfonate; 6-allyoxyhexane-1,2,3,4,5-penta(poly)oxyethylene ether hexane; 6-allyoxyhexane-1,2,3,4,5-penta(poly)oxypropylene ether hexane; 3-allyoxy-2-hydroxypropanesulfonic acid, and its monovalent metal salts, divalent metal salts, ammonium salts, or organic amine salts, or their phosphates or sulfonates, or their monovalent metal salts, divalent metal salts, ammonium salts, or organic amine salts; 3-allyoxy-2-(poly)oxyethylene propanesulfonic acid, and its monovalent metal salts, divalent metal salts, ammonium salts, or organic amine salts, or their phosphates or sulfonates, or their monovalent metal salts, divalent metal salts, ammonium salts, or organic amine salts; and 3-allyoxy-2-(poly)oxypropylene propanesulfonic acid, and its monovalent metal salts, divalent metal salts, ammonium salts, or organic amine salts, or their phosphates or sulfonates, or their monovalent metal salts, divalent metal salts, ammonium salts, or organic amine salts.
The novel water-soluble copolymer in the present invention is obtained by carrying out a copolymerization of comonomers essentially including the unsaturated monocarboxylic acid monomer (1), the unsaturated dicarboxylic acid monomer (2a) and/or (2b), and the unsaturated alcoholic monomer (3). The method for the copolymerization is not especially limited. For example, the copolymerization can be carried out by conventional methods. Examples thereof include a polymerization in solvents such as water, organic solvents, or solvents mixed with water-soluble organic solvents and water. Usable catalyst systems in these polymerizations are not especially limited. Examples thereof include persulfates or hydrogen peroxide, and they can be used together with promoters such as hydrogen sulfrates and ascorbic acid. Besides, azo initiators or organic peroxides can be used and promoters such as amine compounds can be used together. The catalyst system using ascorbic acid together with hydrogen peroxide is preferable because of carrying out the reaction favorably. In addition, the catalyst system using hydrogen peroxide together with at least one metal ion selecting from the group consisting of an iron ion, an ion including vanadium, and a copper ion is more preferable. In addition, chain transfer agents such as mercaptoethanol, mercaptopropionic acid, and hypophosphorous acid sodium salt can be used together as an agent for adjusting molecular weight.
When copolymerizing the comonomers essentially including the unsaturated monocarboxylic acid monomer (1), the unsaturated dicarboxylic acid monomer (2a) and/or (2b), and the unsaturated alcoholic monomer (3) in order to obtain the novel water-soluble copolymer according to the present invention, the ratio of each monomer (monomers (1) to (3), and the above other monomers if necessary) is not especially limited because the ratio can be varied due to the use of the copolymer. For example, the ratio of the total of the unsaturated monocarboxylic acid monomer and the unsaturated dicarboxylic acid monomer is preferably not less than 5 weight %, more preferably 20 weight %, still more preferably 30 weight %. In addition, the ratio is preferably not less than 50 weight % when the chelating ability is more highly requested.
In addition, the ratio between the unsaturated monocarboxylic acid monomer and the unsaturated dicarboxylic acid monomer is not especially limited, but the ratio is preferably in the range of (1 to 99)/(99 to 1) (weight ratio) as the unsaturated monocarboxylic acid monomer/the unsaturated dicarboxylic acid monomer, more preferably (20 to 90)/(80 to 10), still more preferably (50 to 90)/(50 to 10).
In addition, the ratio of the unsaturated alcoholic monomer is also not especially limited, but the ratio is preferably not less than 5 weight %, more preferably 20 weight %, still more preferably 40 weight %. In addition, the ratio is preferably not less than 50 weight % when the compatibility with such as liquid detergents is needed.
The novel water-soluble copolymer according to the present invention is a novel copolymer obtained by copolymerizing the comonomers essentially including the unsaturated monocarboxylic acid monomer (1), the unsaturated dicarboxylic acid monomer (2a) and/or (2b), and the unsaturated alcoholic monomer (3) in the above way, but the copolymer is further characterized in that: the residual amount of the unsaturated dicarboxylic acid monomer is not more than 8 weight %, and the residual amount of the unsaturated alcoholic monomer is not more than 45 weight %. When the residual amounts of the unsaturated dicarboxylic acid monomer and the unsaturated alcoholic monomer are in the above level, the copolymer can display still more excellent performance for uses, such as detergent builders, pigment dispersants, and scale inhibitors than conventional ones.
The residual amount of the unsaturated dicarboxylic acid monomer is preferably not more than 5 weight %, more preferably not more than 2 weight %.
The residual amount of the unsaturated alcoholic monomer is preferably not more than 20 weight %, more preferably not more than 10 weight %, still more preferably not more than 5 weight %.
In case where the residual amount of the unsaturated dicarboxylic acid monomer is more than 8 weight %, there are disadvantages in safety. In addition, the chelating ability and dispersibility are lowered because the content of the carboxylic acid is decreased in the copolymer. In addition, when the copolymer is used in an aqueous state, there are disadvantages in that the residual unsaturated dicarboxylic acid monomer may be insoluble depending on pH of the liquid.
In case where the residual amount of the unsaturated alcoholic monomer is more than 45 weight %, the performance such as dispersibility and compatibility with liquid detergents is lowered because the effective content is decreased in the copolymer. In addition, there are disadvantages in that the copolymer can be changed with the passage of time because the unsaturated alcoholic monomer is reactive.
Another novel water-soluble copolymer, according to the present invention, is a novel copolymer obtained by copolymerizing the comonomers essentially including the unsaturated monocarboxylic acid monomer (1), the unsaturated dicarboxylic acid monomer (2a) and/or (2b), and the unsaturated alcoholic monomer (3) in the above way, but the copolymer is further characterized by having a clay dispersibility (50 ppm of calcium carbonate) of not less than 0.7. When the clay dispersibility (50 ppm of calcium carbonate) is not less than 0.7, the copolymer can display still more excellent performance for uses, such as detergent builders, pigment dispersants, and scale inhibitors than conventional ones.
The clay dispersibility (50 ppm of calcium carbonate) is preferably not less than 0.8, more preferably not less than 0.9, still more preferably not less than 1.0.
The novel water-soluble copolymer according to the present invention can be used for the following various uses by itself. However, the copolymer can be used after neutralizing it with an alkaline substance if necessary. Examples of such an alkaline substance include: hydroxides, chlorides, or carbonates of monovalent or divalent metals; ammonia; and organic amines.
The novel water-soluble copolymer according to the present invention can be used for various uses including the following major uses. Examples thereof include water slurry dispersants for inorganic pigments, cement additives, scale inhibitors, detergent builders, deinking agents of waste paper, chelating agents, various dye dispersants, dispersants for agricultural chemicals, cotton scouring-washing agents, and coal dispersants.
The novel water-soluble copolymer, according to the present invention, is a copolymer having excellent clay dispersibility (50 ppm of calcium carbonate) due to the specific copolymerization structure and the residual amount of the monomers in not more than the predetermined level. The clay dispersibility (50 ppm of calcium carbonate) is preferably not less than 0.3, more preferably not less than 0.5, still more preferably not less than 0.7, particularly preferably not less than 0.9.
The novel water-soluble copolymer, according to the present invention, is a copolymer having excellent calcium ion scavengeability due to the specific copolymerization structure and the residual amount of the monomers in not more than the predetermined level. The calcium ion scavengeability is preferably not less than 60 mg/g, more preferably not less than 100 mg/g, still more preferably not less than 130 mg/g, particularly preferably not less than 170 mg/g.
[Production Process for the Novel Water-Soluble Copolymer]
The production process for the novel water-soluble copolymer, according to the present invention, is a production process for the novel water-soluble copolymer essentially comprises a constitutional unit (4), a constitutional unit (5) and a constitutional unit (6) as mentioned above, and is characterized by carrying out a copolymerization of comonomers essentially including the unsaturated monocarboxylic acid monomer (1), the unsaturated dicarboxylic acid monomer (2a) and/or (2b), and the unsaturated alcoholic monomer.
The method for the copolymerization is not especially limited. For example, the copolymerization can be carried out by conventional methods. Examples thereof include a polymerization in solvents such as water, organic solvents, or solvents mixed with water-soluble organic solvents and water. Usable catalyst systems in these polymerizations are not especially limited. Examples thereof include persulfates or hydrogen peroxide, and they can be used together with promoters such as hydrogen sulfrates and ascorbic acid. Besides, azo initiators or organic peroxides can be used and promoters such as amine compounds can be used together. The catalyst system using ascorbic acid together with hydrogen peroxide is preferable because of carrying out the reaction favorably. In addition, the catalyst system using hydrogen peroxide together with at least one metal ion selecting from the group consisting of an iron ion, an ion including vanadium, and a copper ion is more preferable.
[Detergent Builder and Detergent Composition]
The detergent builder according to the present invention is characterized by essentially including the novel water-soluble copolymer according to the present invention.
For example, the detergent builder according to the present invention may consist of the novel water-soluble copolymer according to the present invention, or may be used together with other conventional detergent builders. In addition, the novel water-soluble copolymer as used for the detergent builder according to the present invention may be a product further neutralized with the alkaline substance in the above way if necessary.
Examples of the above other detergent builders include: sodium tripolyphosphate, sodium pyrophosphorate, sodium silicate, sodium sulfate, sodium carbonate, sodium nitrirotriacetate, sodium or potassium ethylenediaminetetraacetate, zeolite, carboxyl derivatives of polysaccharide, water-soluble polymers such as (meth)acrylic acid (co)polymer salts and fumaric acid (co)polymer salts.
The detergent builder according to the present invention may be used for liquid detergents or powdery detergents. However, if the detergent builder is used for liquid detergent compositions, there are advantages in that: the detergent builder has excellent compatibility with the following surfactants, and the liquid detergent compositions are concentrated.
The detergent composition according to the present invention is characterized by comprising the detergent builder essentially including the novel water-soluble copolymer according to the present invention.
The detergent composition according to the present invention usually comprises a detergent surfactant in addition to the novel water-soluble copolymer according to the present invention.
The surfactant is at least one type selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. These surfactants may be used either alone respectively or in combinations of each other.
Examples of the anionic surfactant are alkylbenzenesulfonic acid salts, alkyl or alkenyl ether sulfuric acid salts, alkyl- or alkenylsulfuric acid salts, xcex1-olefinsulfonic acid salts, xcex1-sulfofatty acids or ester salts thereof, alkanesulfonic acid salts, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylic acid salts, amino acid type surfactants, N-acylamino acid type surfactants, alkyl- or alkenylphosphoric acid esters or salts thereof.
Examples of the nonionic surfactant are polyoxyalkylene alkyl or alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerol monoesters, alkylamine oxides.
Examples of the cationic surfactant thereof are quaternary ammonium salts.
Examples of the amphoteric surfactant are carboxyl type or sulfobetaine type amphoteric surfactants.
The content of the surfactant as contained in the detergent composition is usually in a range of 10 to 60 weight %, preferably, 15 to 50 weight %, of the liquid detergent composition. In the case where the content of the surfactant is less than 10 weight %, the sufficient washability cannot be displayed. On the other hand, in the case where the content of the surfactant is more than 60 weight %, the economic advantage is lowered.
The content of the present invention detergent builder as contained in the detergent composition is usually in a range of 0.1 to 60 weight %, preferably, 3 to 30 weight %, of the detergent composition. In the case where the content of the detergent builder is less than 0.1 weight %, the sufficient washability cannot be displayed. On the other hand, in the case where the content of the detergent builder is more than 60 weight %, the economic advantage is lowered.
Various additives which are usually used for detergents can be added to the detergent composition according to the present invention. Examples thereof include: sodium carboxymethyl cellulose for inhibiting reattachment of contaminations, contamination inhibitors such as benzotriazole and ethylene-thiourea, alkaline substances for adjusting pH, perfumes, fluorescent agents, colorants, foaming agents, foaming stabilizers, polishing agents, sterilizers, bleachers, enzymes, dyes, and solvents.
The detergent composition according to the present invention may be used for liquid detergents or powdery detergents. However, if the detergent builder is used for the liquid detergent compositions, there are advantages in that: the detergent builder has excellent compatibility with the following surfactants, and the liquid detergent compositions are concentrated.
[Pigment Dispersant]
The pigment dispersant according to the present invention is characterized by essentially comprising the novel water-soluble copolymer according to the present invention.
The pigment dispersant according to the present invention can be used for dispersing pigments, such as kaolin, clay, calcium carbonate, titanium dioxide, barium sulfate, satin white, and magnesium hydroxide, into water.
The ratio of the pigment dispersant to the pigment is preferably in the range of 0.01 to 3.0 parts by weight of 100 parts by weight of the pigment.
The pigment dispersant according to the present invention has excellent dispersibility and low viscosity even in a high concentration, and enables to produce a dispersing liquid having excellent stability because of essentially comprising the novel water-soluble copolymer according to the present invention. Therefore, the pigment dispersant not only can particularly preferably be used as a dispersant in order to disperse pigments for paper, but also can widely be applied to fields such as fiber processing, building materials processing, paints, and ceramic industries.
[Scale Inhibitor]
The scale inhibitor according to the present invention is characterized by essentially comprising the novel water-soluble copolymer according to the present invention.
For example, the scale inhibitor according to the present invention may consist of the novel water-soluble copolymer according to the present invention, or can be combined with other additives which are used in this technical field. In addition, the novel water-soluble copolymer as used for the scale inhibitor according to the present invention may further be neutralized with alkaline substances if necessary.
The other additives are not especially limited, but the scale inhibitor can be used as a water-treating agent composition by combining with anticorrosive agents such as polymerized phosphoric acid salts, phosphoric acid salts, phosphonic acid salts, zinc salts, and molybdates. In addition, the scale inhibitor can be combined with slime controlling agents or chelating agents if necessary.
The scale inhibitor according to the present invention can be used in the same way as of conventional scale inhibitors, by such as definite or intermittent injection in order to adjust constant concentration in circulating water. When the amount as added is generally in the range of 1 to 50 ppm, the sufficient effects are observed. However, the amount is not limited to the above range.
[Liquid Detergent Builder]
The liquid detergent builder according to the present invention is characterized by including the water-soluble copolymer as an essential component. The water-soluble copolymer obtained by copolymerizing comonomers essentially including an unsaturated carboxylic acid monomer (a) and an unsaturated alcoholic monomer (3), wherein the unsaturated carboxylic acid monomer (a) is any one of an unsaturated monocarboxylic acid monomer (1), an unsaturated dicarboxylic acid monomer (2a), and an unsaturated dicarboxylic acid monomer (2b).
Preferred modes for the water-soluble copolymer are fundamentally the same as of the above water-soluble copolymer according to the present invention. However, when copolymerizing the comonomers essentially including the unsaturated carboxylic acid monomer (a) and the unsaturated alcoholic monomer (3) in order to obtain the water-soluble copolymer in the present invention, the ratio between the monomer (a) and the monomer (3) each in the comonomers is in the range of (5 to 95)/(95 to 5) (weight ratio) as the monomer (a)/the monomer (3). The ratio is preferably in the range of (10 to 70)/(90 to 30), more preferably (20 to 60)/(80 to 40). In case where the ratio of the monomer (a) is less than 5, the chelating ability is lowered. On the other hand, in case where the ratio of the monomer (3) is less than 5, the scale resistance which is an effect of introducing polyethylene glycol chains is lowered.
For example, the liquid detergent builder according to the present invention may consist of the above water-soluble copolymer, or may be used together with other conventional detergent builders. In addition, the water-soluble copolymer as used for the liquid detergent builder according to the present invention may be a product further neutralized with the alkaline substance in the above way if necessary.
Examples of the above other detergent builders include: sodium tripolyphosphate, sodium pyrophosphorate, sodium silicate, sodium sulfate, sodium carbonate, sodium nitrirotriacetate, sodium or potassium ethylenediaminetetraacetate, zeolite, carboxyl derivatives of polysaccharide, water-soluble polymers such as (meth)acrylic acid (co)polymer salts and fumaric acid (co)polymer salts.
When the liquid detergent builder according to the present invention is used for the following liquid detergent composition, the builder is very excellent for a liquid detergent because it has excellent compatibility with surfactants and the liquid detergent composition is concentrated. The transparency of the liquid detergent composition is good and the problem of separating liquid detergents due to muddiness can be prohibited because the builder has excellent compatibility with surfactants. Then, the excellent compatibility can make a concentrated liquid detergent composition, and leads the improvement of detergency of the liquid detergent.
The liquid detergent builder according to the present invention is a copolymer having an excellent clay dispersibility (50 ppm of calcium carbonate) of not less than 0.3, preferably not less than 0.5, more preferably not less than 0.7, particularly preferably not less than 0.9, because it comprises the above specific water-soluble copolymer. In case where the builder has a clay dispersibility (50 ppm of calcium carbonate) of less than 0.3 and used as a liquid detergent builder, there are disadvantages in that the effects of improving detergency against mud dirt are particularly lowered.
[Liquid Detergent Composition]
The liquid detergent composition according to the present invention is characterized by comprising the liquid detergent builder according to the present invention.
Because the present invention liquid detergent builder comprised in the present invention liquid detergent composition has excellent compatibility with surfactants, the transparency of the liquid detergent composition is good and the problem of separating liquid detergents due to muddiness can be prohibited. Then, the excellent compatibility can make a concentrated liquid detergent composition, and leads the improvement of detergency of the liquid detergent.
The turbidity (kaolin turbidity) measured with a turbidmeter is useful as one of scales which represent excellent compatibility. The turbidity value of the liquid detergent composition according to the present invention is preferably not more than 200 mg/l at 25xc2x0 C., more preferably not less than 100 mg/l, still more preferably not less than 50 mg/l.
The liquid detergent composition according to the present invention can display excellent detergency in comparison with conventional liquid detergent compositions because it comprises the liquid detergent builder which can give excellent detergency.
The liquid detergent composition according to the present invention usually comprises a detergent surfactant in addition to the liquid detergent builder according to the present invention. The detergent surfactants as mentioned above can be used.
The combining ratio of the surfactant and the detergent builder in the liquid detergent composition according to the present invention, and additives which can be added are in the same as of the above detergent composition according to the present invention.
(Effects and Advantages of the Invention):
The present invention can provide: a novel water-soluble copolymer which is still more excellent in performance for uses, such as detergent builders, pigment dispersants, and scale inhibitors.
The present invention can provide: a novel liquid detergent builder which has extremely excellent compatibility, high transparency when a liquid detergent composition comprises it, and very excellent detergency; and a novel liquid detergent composition comprising the liquid detergent builder.
Hereinafter, the present invention is more specifically illustrated by the following examples of some preferred embodiments in comparison with comparative examples not according to the invention. However, the present invention is not limited to the below-mentioned examples.
Incidentally, the weight-average molecular weight of the polymer as obtained in the following examples or comparative examples was measured in the following way.
(Measurement of Solid Content)
The solid content denoted nonvolatile content obtained by drying with hot-blow dryer at 110xc2x0 C. for 2 hours.
(Measurement of Acid Value)
The acid value was measured by a titration using an aqueous sodium hydroxide solution of 1 N. When the copolymer was not in an acid form, the acid value was measured by a back titration using an aqueous hydrogen chloride solution of 1 N.